Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
  • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M149/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
  • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
  • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group

Definitions

• the invention relates to a graft polymer consisting of a hydrogenated olefin / diene backbone polymer onto which allylamine is grafted.
• common lubricant formulations today contain, in addition to various other additives, also dispersants, which have the task of oil-insoluble combustion residues, which can be up to 10% by weight in diesel engines (soot, coke, etc.) and resin and asphalt-like oxidation products that promote caking to solid particles ), in suspension and thereby prevent deposits on metal surfaces, oil thickening and sludge deposits in the engine, as well as through neutralization of acidic combustion products, corrosive wear (see e.g. NJH Small in catalysts, surfactants and mineral oil additives, published by J. Falbe and U Hasserodt, G. Thieme Verl. Stuttgart 1978).
• dispersants which have the task of oil-insoluble combustion residues, which can be up to 10% by weight in diesel engines (soot, coke, etc.) and resin and asphalt-like oxidation products that promote caking to solid particles ), in suspension and thereby prevent deposits on metal surfaces, oil thickening and sludge deposits in the engine, as
• dispersants are necessarily polar compounds or at least contain a sufficient number of polar groups in the molecule, the polar properties of the dispersants can compete with properties of the generally nonpolar VI improvers, e.g. mutual negative influence of the solubility or swellability in the lubricating oil can occur.
• VI improvers with dispersing action have already been proposed (see, for example: Chem. Technol. Rev. No. 207, p. 225 ff., NDC, New Jersey, 1982).
• Examples are polymers and copolymers with acyl groups of different compositions which have been reacted with reagents containing amino groups (US Pat. No. 4,735,736; US Pat. No. 4,670,173) or polymers modified with amines based on various polymers and copolymers (US Pat. No. 4,715,975; EP 171 167). called.
• the ratio of an amine-containing unit (allylamine) per unit of the backbone polymer (i.e. ethylene or propylene) is 1: 100 to 300, preferably 200.
• the object was therefore to propose graft polymers which have fewer amino groups, i.e. have an overall lower nitrogen content and have an unchanged good or even better effect as a VI improver and dispersant.
• graft polymers containing amino groups consisting of a framework polymer onto which allylamine is grafted, in which the framework polymer is a hydrogenated olefin / diene copolymer and the total nitrogen content of the graft polymer is 0.001 to 0.05% by weight.
• graft polymers of the type mentioned in which the backbone polymer is a hydrogenated styrene / butadiene random copolymer with a styrene / butadiene ratio of 60 to 40 to 50 to 50, one molecular weight (weight average) from 5000 to 500,000 and a degree of hydrogenation from 95 to 99.5.
• the starting materials for the backbone polymer are generally hydrogenated olefin / diene copolymers, which are known as VI improvers with particularly high shear stability.
• Vinyl aromatics such as styrene, ⁇ -methylstyrene, nuclear methylated or alkylated styrenes are usually used as olefin comonomers, but preferably unsubstituted styrene.
• conjugated diene comonomers examples include chloroprene, 2,3-dimethyl-1,3-butadiene, isoprene and 1,3-butadiene, the latter two being used with preference. Mixtures are also possible.
• copolymers can be either randomly or in blocks, linear or branched, stoichiometric or in excess with one of the components, the proportion of vinylaromatic being between 20 and 80%, preferably between 40 and 60%.
• the average molecular weights (weight average) of such copolymers are between 10,000 and 200,000, preferably between 80,000 and 120,000.
• the remaining portion of unsaturated units is between 0.2 and 4% based on the diene portion, but preferably not more than about 0.5% or in other words, the degree of hydrogenation (ie as a percentage of the maximum possible saturation of the remaining olefinic double bonds) 96 to 99.5%.
• An example of a hydrogenated random styrene / butadiene copolymer is a product with a mass ratio of styrene to butadiene of 57:43, a weight average molecular weight of 110,000 and a degree of hydrogenation of 99.5%.
• Reaction and framework polymers with allylamine in the presence of radical initiators make it possible to produce graft copolymers with different nitrogen contents.
• the grafting reaction can be carried out in a manner known per se, e.g. the framework polymer in a hydrocarbon solvent, such as hexane or cyclohexane, is initially introduced together with the allylamine and a radical initiator is added all at once or continuously at a higher temperature, generally at the reflux temperature of the solvent, generally choosing a reaction temperature which is below that for the chosen initiator remains optimal radical formation temperature.
• a hydrocarbon solvent such as hexane or cyclohexane
• the initiators are e.g. Azoisobutyronitrile, peroxides, hydroperoxides and related compounds known as initiators are contemplated.
• the reaction can be carried out in the presence of a regulator, such as mercaptoethanol, dodecyl mercaptan and
• graft component allylamine based on the olefin content, ie styrene content of the framework polymer, is also sufficient, which in turn can have a regulating effect in the sense of preventing crosslinking.
• the work-up can be carried out by removing the solvent and the excess allylamine by distillation or adding a suitable oil as the final solvent before removing the volatile constituents or by first treating the reaction solution with suitable washing solutions (saturated ammonium chloride solution, sodium hydrogen sulfate solution, then Water) and freed of volatile components after drying with common desiccants. If the grafting was carried out in emulsion, methods which are known per se, e.g. Denaturation or coagulation, worked up.
• Suitable mineral lubricants are conventional hydrocarbons used for lubricating oils, which are obtained from naturally occurring, paraffinic or naphthenic petroleum by distillation and subsequent refining.
• the mineral lubricating oil compositions can also contain other known additives, e.g. Contain antioxidants, pour point depressants, dyes, detergents, etc.
• the graft copolymers are dissolved in amounts of 0.5 to 6, preferably 1 to 5,% by weight in the mineral oil at 80 to 130 ° C.
• a) 200 parts of a hydrogenated styrene / butadiene copolymer with a mass ratio of styrene to butadiene of 57 to 43 and an average molecular weight of 100,000 to 110,000 are dissolved in 1000 parts of cyclohexane. 40 parts of allylamine are added and the mixture is heated under reflux under a nitrogen atmosphere.
• the polymer After removal of the solvent and volatile constituents and, if appropriate, the excess allylamine, the polymer is obtained as a residue with a total nitrogen content of 0.006% by weight.
• a spot test can be used as a preliminary test, as described, for example, by A. Schilling in "Les Huiles pour Moteurs et le Graissage des Moteurs, Vol. 1, 1962, page 89 f. in a slightly modified form is described.
• a solution of the polymer obtained under a) is prepared in an unalloyed base oil, in which carbon black (for example: MT carbon black Thermax, Lehmann & Voss & Co., Hamburg) is then stirred at about 50 ° C. for one hour dispersed. This dispersion is developed on a flow paper (filter paper) like a chromatogram for about 20 hours.
• carbon black for example: MT carbon black Thermax, Lehmann & Voss & Co., Hamburg
• soot carrying capacity is naturally dependent on the concentration of the additive and also on the viscosity of the base oil: oil polymer Polymer content% Soot content% Area percent soot% NIA - - 0.36 8th NIA Framework polymer according to example a) 1.5 0.36 42 NIA Graft polymer according to Example a) 1.5 0.36 68 NIIA - 0.36 16 NIIA Framework polymer according to example a) 1.5 0.36 58 NIIA Graft polymer according to Example a) 1.5 0.36 63

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Graft Or Block Polymers (AREA)
• Lubricants (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 1989
  • 1989-04-05 DE DE3910943A patent/DE3910943A1/de not_active Withdrawn
• 1990
  • 1990-04-02 DE DE9090106260T patent/DE59001826D1/de not_active Expired - Lifetime
  • 1990-04-02 EP EP90106260A patent/EP0391297B1/fr not_active Expired - Lifetime
  • 1990-04-04 CA CA002013846A patent/CA2013846A1/fr not_active Abandoned
  • 1990-05-08 US US07/504,485 patent/US5026494A/en not_active Expired - Fee Related

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